International Journal of Advanced Research and Publications

ISSN: 2456-9992

Analysis Of Selected Trace Metals From Oil

(Petroleum Products) In A Polluted Soil (A Case
Study Of Offa Local Government Area
ADEYEMI, Christianah. Oluwakemi., GIRIGISU, Sadisu., SHITTU, Fatimah. Bukola., IBITOMI, O. O,
OYEDEJI Oyedoyin Bukola
Federal polytechnic Offa, Kwara State, Nigeria, School of Applied Sciences and Technology, Science Laboratory Technology Department

Bowen University Advanced Level Programme, Osun State, Nigeria Phone number: 08038076576
Christianaholuwakemi02@gmail.com, girigisusadisu@yahoo.co.uk, shittufb@gmail.com, ibitomioluyemiolasumbo@gmail.com,
oyedoyinbukola@yahoo.com, christianaholawale@ymail.com

ABSRACT: The concentrations of heavy metals (Fe, Cu, Cr, Pb and Ni) in soil samples of filling stations and those of a control area
(about a kilometer away from the filling stations) were investigated by sequential extraction method using Atomic Absorption Spectrometer
(AAS). Results obtained showed the mean concentrations (mg/kg) of Fe, Cu, Cr, Pb and Ni in soil of studied areas as 18.43, 0.01, 0.012,
0.02, and 0.01 respectively while in controlled area soil are Fe, Cu, Cr, Pb and Ni had concentrations (mg/kg) of 10.376, 0.007, 0.004, 0.005
and 0.0048 respectively. Levels of the heavy metals in soils of both studied areas were observed to be lower than European Union safe
limits.

Keywords: Heavy metals, soil, Concentrations, Atomic Absorption Spectrometer.

1.0 INTRODUCTION
Oil is defined as a broad range of hydrocarbon-based
substances, which are of two types: mineral oil such as
different specific distillates of crude oil, and organic oil
such as animal fats and vegetable oils. Natural gas, crude
oil, tars and asphalts are types of petroleum hydrocarbons
[1]
.The word "petroleum" means "rock oil" or "oil from the
earth" [2]. Petroleum widely used in our daily life plays a
vital role in our modern economy. We are dependent on it in
many ways as it provides great benefits to society. It is not
only the main energy source for heating, transportation and
manufacturing, but also acts as a raw material for plastics
and synthetic rubber [3]. Petroleum hydrocarbons (PHCs) are
used to describe mixtures of organic compounds found in or
derived from geological substances such as oil, bitumen and
coal [4].They are composed of two categories: Gasoline
range organics which refers to small chain alkanes (C6-
C10), e.g. methane, ethane, propane, volatile aromatic
compounds (e.g. BTEX) and common oxygenates (e.g.
MTBE and ethanol) and Diesel range organics are the
alkanes with longer chains (C10-C40) or non- halogenated
semi-volatile organic compounds and hydrophobic
chemicals such as PAHs (e.g. naphthalene, phenanthrene,
anthracene, benzopyrene) [5] [1].The small chain alkanes,
such as isopentanes, always have low boiling point between
60 and 170⁰C Pollution is defined by Robert (1971)[6]“as the
contamination of the environment with any material or state
of condition that create a stress on or unfavorable situation
of an individual or organism, population, community or
ecosystem beyond what is found in natural environment
condition”. Nest (1982)[7] defined environmental pollution
as “an undesirable change in the physical and biological
characteristics of our air, land, water that may adversely
affect human living conditions. Any situation which
therefore disturbs in anyway the condition under which any
person or thing lives or develop and hamper the
development of life and character is environmental pollution
[8]
. Contamination of heavy metals in the environment has
been shown to be of major concern because of their toxicity
and threat to human life and the environment. Several
studies have been carried out on trace elements
contamination in soils from various anthropogenic sources
such as industrial wastes[9].
2.0 LITERATURE REVIEW
Adverse effects of crude oil contamination of the natural
environment include the poisoning of animals and plants,
altering of ecosystems, and the potential risk to human health
if the contaminated product is ingested. Again, owing to their
chemical structure, many synthetic organic compounds could
be extremely resistant to natural breakdown processes.
Therefore, when released into the environment, they may
persist for years and even decades[10]. Volatile organic
compounds (VOCs) are vapours emitted by various
petroleum products, cleaning supplies and adhesives many of
which have short- and long-term adverse health effects. The
volatilization from contaminated materials can release
substantial amounts of hydrocarbons up to 30 ppm (Akutam,
2012)[11] and contribute significantly to environmental
degradation. The aromatic compounds which can induce
carcinogenic and mutageni creactions are particularly
problematic because they pose serious health challenges for
the population [11]. Groundwater is one of the many media
through which human beings, plants and animals come into
contact with petroleum hydrocarbon pollution [12].The major
concern therefore is its contamination potential and the
challenge posed to clean-up. The poor miscibility of crude
oil accounts for the accumulation of free oil on the surface of
ground water and this may migrate laterally over a wide
distance to pollute other zones very far away from the point
of pollution [13]. In environments that are completely aquatic,
oil sometimes floats on water surfaces where it is dispersed
to shorelines by wind and wave actions invariably affecting
the mangrove floor [14]. Furthermore, due to the release of
mineral oil hydrocarbons (MOH), phenol, and polycyclic
aromatic hydrocarbons (PAHs) often rich inlarge amounts of
tar; drinking water supplies have been endangered and often
polluted [13]. Crude oil spills have been reported to affect soil

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992

fertility but the scale of impact depends on the quantity and distilled water and were filtered, the filtrates were made up
type of oil spilled. Spent engine oil also, when present in the to 25 ml with distilled water and were transferred into the
soil, creates an unsatisfactory condition for organic life in the apspropriate sample bottles. The concentration of trace
soil due to the poor aeration condition established therein, metals Cr, Cu, Zn, Fe, Pb, Ni, and Cd was then determined
immobilization of soil nutrients, and the lowering of soil pH using Atomic Absorption Spectrometer (AAS).
[15]
. Petroleum hydrocarbons contamination has also been
reported to affect plants by retarding seed germination and 4.0 RESULTS AND DISCUSSION
reducing shoot height, stem density, photosynthetic rate and
over all biomass yield (in the short run), and resulting in RESULTS
complete mortality in the long run,[16, 17, 18].On land, crude oil 4.1. Heavy Metals determination
spills have caused great negative impact on food production. The results of elemental analysis of soils at the three
For example, an appreciable percentage of oil spills that locations and controlled area is summarized in Table 1
occurred on the dry land between 1978and 1979 in Nigeria,
affected farmlands in which crops such as rice, maize, yams, Table 1: Concentrations of Heavy Metals in Study Area
cassava, plantain and other staples were cultivated and since (Mg/g)
this infraction has persisted till date, anticipated yields from
harvest have remained largely illusive and so is food security (Cu) (Cr) (Pb) (Ni)
Locations (Fe) mg/g
in the zone of contamination. This invariably has shot up mg/g mg/g mg/g mg/g
commodity prices and has also reduced living standards [19]. A1 25031.31 16 20 31.25 6.12
A2 15656.37 10.25 6.25 13 4.75
Again, because many toxic synthetic organic compounds are A3 14593.87 10.25 9.37 19.87 2.75
persistent in nature, when ingested by organisms at higher Control 10376.75 7.0 4.75 5.125 2.75
levels of the food chain, they tend to be stored in the fatty
tissues due to their hydrophobic properties resulting in Table 2: Mean concentration of Heavy Metals in Study
bioaccumulation [20]. These researchers also reported that Areas& EU Standards (mg/kg)
PAHs and BTEX components of petroleum hydrocarbons
have also been observed to affect the liver, lungs, kidneys
and nervous system leading to cancer as well as (Fe) (Cu) (Cr) (Pb) (Ni)
Locations
immunological, reproductive, feto-toxic and geno-toxic mg/kg mg/kg mg/kg mg/kg mg/kg
effects or Biomagnifications. This may arise as a result of the
physiological effects of the toxins in higher organisms.
A1 25.03 0.017 0.02 0.03 0.02
Again, at the highest level of the food chain, i.e. humans,
these toxic organic compounds can be passed from mother to
A2 15.65 0.01 0.006 0.01 0.04
child either in uterus via the placenta orpost-natally via
breast milk if ingested [21]. Crude oil spilled into mangrove
environments under the tidal influences that characterize the A3 14.59 0.010 0.009 0.01 0.003
marine ecosystem provides for wider dispersal and
distribution in the intertidal flats (zones) resulting in the Control 10.37 0.007 0.004 0.05 0.003
deposition of crude oil and or other petroleum products on
the aerial roots and sediments [22]. Thus, crude oil covers the
EU
breathing roots and pores, thereby asphyxiating the sub- Standard
1500 20-30 100 90-300 50.0
surface roots that depend on the pores for oxygen transfer
and in turn impairs the normal salt exclusion process
resulting in the accumulation of excess salt in the plant Table 3: Mean Concentrations of heavy metals in control
thereby contributing to an enhanced stress condition of the area mg/g.
plant and ultimately, to death/loss of mangrove plants,
habitat destruction and degradation [21].
(Fe) mg/g (Cu) mg/g (Cr) mg/g (Pb) mg/g (Ni) mg/g
3.0 MATERIALS AND MEHTHODS
3.1 Triplicate of soil sample were collected each at a depth of 18427.19 12.17 12.00 21.38 4.54
0.20cm with a stainless steel spoon from three different
points of petrol stations. The distance from one sampling Table 4: Mean Concentrations of heavy metals in control
point to other was 10 meters. Controlled soil samples(soil area mg/kg.
without petrol) was also sample in triplicate from three
different points of controlled area of about 500m away from (Fe) mg/kg (Cu) mg/kg (Cr) mg/kg (Pb) mg/kg (Ni) mg/kg
18.43 0.01 0.012 0.02 0.01
the petrol stations. A polythene bag was used for sample
storage.
Table 1 shows the concentrations of heavy metals (iron,
3.2 Soil samples were air dried in the laboratory at room
copper, chromium, lead and nickel) in mg/g in the soil
temperature and sieved with a 200 mm to remove stones and
samples of various petrol filling stations and the controlled
fragments, was later dried at 1050C in an oven and crushed
area, while table 2 shows the concentration in mg/kg and
into fine powder.
table 3 & 4 shows the mean concentrations of heavy metals
3.3 2.0 g of the samples were weighed into four different
in the soil samples. The metal content in the soil varied
beakers and 10 ml of HNO3 and 5 ml of HCl was added to
significantly from one sampling location to another and was
each samples on a hot plate and were allowed to digest for 3
also compared with the controlled area results . Iron (Fe)
hours, the digested samples were diluted with 10 ml of

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992
content ranged from 14.59-25.03 mg/kg, Copper (Cu)
ranged 0.01-0.02 mg/kg. Chromium (Cr) ranged from
0.009-0.02 mg/kg, Lead (Pb) ranged from 0.01-0.03 mg/kg
while Nickel (Ni) ranged from 0.00-0.04 mg/kg. In this
research the levels of concentration in increasing order Fe >
Pb > Cu > Cr > Ni. The concentrations were lower than
European Commission (EU limits) of 15000 mg/kg, 100
mg/kg, 100 mg/kg, 90-300 mg/kg and 50 mg/kg
respectively. While the concentration in the control area are
Fe 10.37 mg/g, Cu 0.007 mg/g, Cr 0.004 mg/kg, Pb 0.005
mg/kg and Ni 0.003 mg/kg which are also lower than EU
limits of 15000mg/kg, 100mg/kg, 100mg/kg, 90-300mg/kg
and 50kg/g respectively [81].
DISCUSSION
Ni concentration from three location range between 0.002-
0.02 mg/kg and that of control area is 0.003 mg/kg which
are lower than the recommended EU standard. The range of
Ni concentration in all the soil samples in this research is
also lower than what obtained in some other studies carried
in the united state (2.44 mg/kg) (Shacklette and Boerngen
1984) [82], China (7.73 mg/kg) (Dudka, 1992), [83] Poland
(2.0mg/kg) (Bradford et al., 1996)[84] Ethiopia (47.3 mg/kg)
(Melaku et al., 2005)[85], and India (343 mg/kg)[86]. Natural
concentration of Nickel in soil is less than 100 mg/kg it can
be exceptionally high in some cases especially the soil
formed from ultra-basic rocks. Diseases related to high level
of heavy metal in system include lung tissue damage
respiratory illness, liver and kidney failure and others. [87] Pb
concentration from the three locations ranged from 0.01-
0.03 mg/kg and that of the control area is 0.005 mg/kg
which are lower than the limit of 90-300 mg/kg
recommended by EU standard. The range of Pb
concentration in all the soil samples in this research is also
lower than what obtained in some studies carried out in
Lagos Metropolis was 69.20 mg/kg. The result of lead
concentration in soil of old industrial cities like Uppsala (in
northern European) have the mean Pb level in playground
soil to be 26 mg/g (Ljung et al., 2006), [88] while cities such
as Hong Kong which have their mean Pb level in
playground soil to be 77.3 mg/kg (Sai et al., 2012) [89]in
(Popoola et al., 2012).[90] These levels may reflect the long
history of industrial contamination complied within traffic
emission because Pb gasoline has been phased out in most
of these countries .[90] The mean concentration obtained in
this research were lower than the range of 30-50 mg/kg
reported by Nrigu (1992)[91] as typical concentration of lead
in urban soils of African cities which gives cause for
concern. However, the source of Pb in the urban could be
more due to oil spillage during storage or rusted of the
storage tanks or leakages. It was revealed by Atunya and
Osegbe (2006)[92] that higher lead concentration in soil has
toxic effect on microorganism inhabiting the soil which
consequently alters the flora and fauna of the location. Lead
has been found to be the major cause of hypertensions,
impairment of central nervous system and other respiratory
problem adult [93]. The upper limit of Cr in this research is
(0.02 mg/kg)and that of the control area is 0.007 mg/kg
which is less than the limit of 100 mg/kg recommend by EU
standard. Trace amount of meta such as trivalent chromium
entering the body through various routes is capable of
inducing genetic and epigenetic alteration in different cancer
related gene somatic and stem cells, thus involving in cancer
stem cell formation and increasing the incidence of cancer
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[90]
. The concentration of Fe for this research ranges from
14.39-25.03 mg/kg and that of control area 10.37 mg/kg
which is lower than what was obtained in Lagos Metropolis.
The concentration was found to be 1528.3 mg/kg Fe has to
be found to occur at high concentration in Nigeria soil
(Adefemi et al., 2007)[94]in Olakanmi and Adeoye (2012)
[95]
, as obtained in his study. The high concentration of these
metals in soil samples may also be due to oils pillage or
leakage of the storage tank in the filling station or the
natural lithogeneric or pedogenic processes (Woodhouse,
1983)[96], as well as anthropogenic factors which result in
environmental pollution [96]. The concentration of Cu in this
research ranged from 0.01-0.02 mg/kg and that of the
control area is 0.007 which has lower than the EU standard
limit 20-30 mg/kg this can be attributed to spill of oil
(petrol, diesel) during the storage or leakage from the
storage tank. Cu is essential element, but may be toxic to
both humans and the animals when its concentration
exceeded the safe limit. Cu is used in numerous applications
because of its physical properties. The toxicity for human is
not very high (Poggio et al., 2009)[97] Cu normally
accumulated in the surface horizons a phenomenon
explained by bioaccumulation of metals and recent observed
values of the Cu content did exceeded the normal threshold
value prescribed in soil 20-30 mg/kg [98]
5.0 CONCLUSION
Speciation analyses give relevant information on the toxicity
and biological activity of elements because the effects of
these elements in soils do not depend on their concentrations
alone, but also on their oxidation states and/or chemical
forms. The results obtained from the sequential analysis of
soils collected filling stations Offa indicated that the
concentrations of Fe, Cu, Cr and Pb and NI were lower than
permissible levels. Generally, the levels of heavy metals in
soils in the study area were observed to be lower than those
of previous studies in industrial and residential areas and also
lower than allowable limits by relevant standard
organizations, this may be due partly to the controlled and
cautious activity of the filling stations.
REFERENCES
[1] Frick, C. M., Farrel, R. E. & Germida, J. J.,(1999).
“Assessment of Phytoremediation in an In-situ
Technique for Cleaning Oil-Contaminated Sites”
Petroleum Technology Alliance Canada (PTAC)
Calgary, AB
[2] U. S. Environmental Protection Agency (USEPA)
(1998). “A Citizens guide Phytoremediation EPA”. 542-
F-98-011, Office of Solid Waste and Emergency
response. Washington DC. 6pp
[3] Lujuan, Y., (2012). “The use of plants including trees to
remediate oil contaminated soil” Department of forest
sci. University of Helsinki. Toxicology and Food Tech.
ISSN: 2319-2402 Vol. [4] Pp. 47-56
[4] Canadian Council of Minister of the Environment
(CCME) (2001). “Canada-wide standards for petroleum
hydrocarbon (PHC) in soil” 8pp
[5] Kamath, R., Rentz, J. A., Schnoor J. L. & Alvares P. J.
J.,(2007). “Phytoremediation of hydrocarbon
259
 International Journal of Advanced Research and Publications
ISSN: 2456-9992

Contaminated Soil” Principle and application
Department of Civil and Environmental Engineering.
Seamanscenter .University of Lowa, Lowa city U.S.A
52242
[6] Robert, K. (1971). “Environmental Resource Pollution
and Society”. Murdoch. New york
[7] NEST (1991). “Nigerian’s Threatened Environment” A
National Profile Intec. Printers Ltd. Ibadan
[8] Ugboma P. P., (2012). “Environmental Pollution in
Relation to Oil Industry” An International Journal of
Science and Technology. Bahir Diary Ethopia Vol. 1 (3)
ISSN 2225-8612
[9] Babatunde O. A., Oyewale, A. O. and Steve P. I., (2008)
“Bioavailable Trace Elements in Soil around NNPC Oil
Depot Jos.” J. of Environmental Sci.Toxicology and
Food Tech. ISSN: 231965. Akutam, A., (2012).
“Screening of some indigenous Cidianian Coastal and
Inland Species for Phytoremediation of Oil
Contaminated soil.” An Mphi thesis of Ghana. (1), 8-37
[10] Akutam, A., (2012). “Screening of some indigenous
Cidianian Coastal and Inland Species for
Phytoremediation of Oil Contaminated soil.” An Mphi
thesis of Ghana. (1), 8-37
[18] Onyefillu, K. O. & Awobajo, O. O. (1979).
“Environmental aspect of the petroleum industry in the
Niger Delta, Problems and solutions” A paper presented
at the an international conference on the Nigeria state,
Oil and Gas Industry and the Niger Delta
[19] Brady, & Duncan (1990)“Technology of Bio sorption”
Retention of Biomass and Mixing with the solution,
381P
[20] McGuinnnes, M.,& Dowling, D., (2009). “Plant
associated bacterial degradation of toxic organic
compound in soils”. International Journal of
Environmental Public Health.2226-2235pp
[21] Akutam, A., (2012). “Screening of some indigenous
Cidianian Coastal and Inland Species for
Phytoremediation of Oil Contaminated soil.” An Mphi
thesis of Ghana. (1), 8-37
[22] Baker, J.M. (1981). “Impact of the petroleum industry
on the mangrove“ A paper presented at the seminar on
the Petroleum industry and the Nigerian Environment.
NNPC/FMW & H, Petroleum Testing, Warri, Nigeria,
71-89Pp.

[11] Joel, O. F. & Amajuoyi, O. A., (2009). “Evaluation of

the Effects of Shot-Term Cadmium, Expose on Brackish
Water Shrimp- Palaemonetesafricaus”. Journal Of
applied science and Environmental Management.13
(14), 23-27

[12] Osuji, L. C., Egbusion, E. J. & Ojinnaka, C. M. (2006).

”Assessment and treatment of hydrocarbon Inundated
soil using inorganic nutrient (N.P.K) supplement”: A
Case study Of Eneke Oil Spillage in Niger Delta Enviro.
Monit. Assess. 115 (1-3), 265-278

[13] Charles O., (2013). “Phytoremediation of Some Tropical

soils Contaminated with Petroleum Crude Oil.”
University of Ghana Legon, Ghana

[14] Atunya, E. I. (1987). “Effect of Waste engine oil

pollution on physical and chemical properties of soil: A
case study of waste oil contaminated Delta soil in
Bendel State. Nigeria. J. Appl. Sci. (5), 155-176

[15] Mendelssohn, I. A., Hester, M. W., Sassar, C. &Fischel

M. (1990). “The effect of Louiisina crude oil discharged
from pipeline break on a Southeast Loiusiana brackish
marsh oil chemical pollution”

[16] Lin, Q. & Mendelssohn, I. A. (1996). “A comparative

investigation an effects of Louisinia crude oil on the
vegetation of fresh water brackish and salt marsh”.
Marine Pollution Bulletin (32) 202-209

[17] Pezeshski, S. R., Hester M. W., Lin, Q. & Nigerian, J.A.

(2002). “The effect of oil spill and clean-up on dominant
US Gulf Coast marsh microphytes”: a review.
Environmental pollution. 108, 129-139

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